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CN1009934B - Olefin polymerization catalyst - Google Patents

Olefin polymerization catalyst

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Publication number
CN1009934B
CN1009934B CN87105136A CN87105136A CN1009934B CN 1009934 B CN1009934 B CN 1009934B CN 87105136 A CN87105136 A CN 87105136A CN 87105136 A CN87105136 A CN 87105136A CN 1009934 B CN1009934 B CN 1009934B
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China
Prior art keywords
catalyst component
magnesium
milliliters
organosilane
component
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Expired
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CN87105136A
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CN87105136A (en
Inventor
格雷戈里·杰拉西莫斯·阿朱曼尼迪斯
布赖斯·文森特·约翰逊
尼古拉斯·马里奥斯·卡拉扬尼斯
哈贝特·M·凯尔加蒂安
萨姆·李石松
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BP Corp North America Inc
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BP Corp North America Inc
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Publication of CN87105136A publication Critical patent/CN87105136A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A solid, hydrocarbon-insoluble alpha-olefin polymerization catalyst component having high activity, high stereospecificity and good morphological characteristics, the catalyst component comprising the product of the following steps: A) preparing a solution containing a magnesium component from magnesium carbonate or magnesium carboxylate; B) treating the magnesium-containing solution with a halide of a transition metal and an organosilane to precipitate solid particles from the solution; C) re-precipitating the solid particles in a mixture containing a cyclic ether; and D) treating the reprecipitated particles with a transition metal compound and an electron donor.

Description

Olefin polymerization catalyst
The application is application on June 17th, 1986, United States Patent (USP) sequence number 875, the part of 180 application cases continues, this application is application on June 6th, 1985, and the United States Patent (USP) sequence number is that the part of 741,858 application cases continues, sequence number is 741,858 application case (now being US4,612,299) is that the part of following two application cases continues:; The United States Patent (USP) sequence number: application on July 9th, 629,106,1984, now cancel; The application on March 23rd, 592,910,1984 of United States Patent (USP) sequence number now is a United States Patent (USP) 4,540,679, and the specification sheets of above-mentioned application and the content of claim are listed the application's case in as cited literature 2.
The invention relates to the catalyst system that is used for alpha-olefine polymerizing, particularly about a kind of halogenated titanium catalyst component and a kind of catalyst system that contains this class component of carrierization.
In the art, the alpha-olefin polymerization catalyst component based on magniferous carrier halogenated titanium is well-known.Particularly because the characteristic of these catalyzer aspect active and stereospecificity, by sure.; in industrialized olefinic polymerization, particularly in the gas phase alpha-olefine polymerizing, also require catalyzer can have other catalysis attribute and bring economic benefit in the production process on a large scale; particularly mainly depending on the polymer morphology of catalyzer form, usually is critical problem.The implication of good polymer morphology is: particulate size and shape homogeneous, abrasion resistance and higher bulk density.The formation that reduces nano sized particles (powder) is particularly important, especially can avoid the obstruction of transmission lines or recirculation circuit in vapour phase polymerization.In reactor, to form agglomerate and fibrous material in order reducing, also will to avoid producing great particle.
The polymkeric substance smallest particles mean diameter that makes with suitable catalyzer should be greater than 150 microns (powder), or less than 850 microns.Another is to keep desirable high bulk density in industrial very important performance, and the poundage of this performance every cubic feet of polymkeric substance commonly used measures.As United States Patent (USP) 4,540, described in 679, a method controlling good form is to make magnesium component solubilizedization with carbonic acid gas in alcoholic solvent.Though provided a highly active catalyzer in the embodiment of this patent VI, owing to produce too many powder, its form needs to improve.
The present invention includes a series of catalyst preparation step, obtain a kind of not only have high reactivity and stereospecificity, the catalyzer that also has good form.
Carrierization, contain magnesium, titaniferous, the olefin polymerization catalysis that contains electron donor is well-known in the art.In the United States Patent (USP) of mentioning in front 4,540,679, once narrated in preparation and used carbonic acid gas during magniferous carrier, in the other document, also mentioned the use of carbonic acid gas, as United States Patent (USP): 4,246,383; 2,244,828; 4,529,715 and 4,530,915.At chemical abstracts, 76 volume 853050V(1972) mentioned alcoholic solution and suspension in carbonic acid gas and sulfur dioxide treatment alkaline earth alcoholate.In United States Patent (USP) 4,315,874; 4,399,054; 4,071,674; With 4,439, narrated in 540 and formed a kind of solvable magnesium component.In United States Patent (USP) 4,071,672; 4,085,276; In 4,220,554 and 4,315,835, used silicon compound during the preparation catalyst component.The effect of tetrahydrofuran (THF) (THF), once set forth in many places: with the complexing of magnesium chloride component (as United States Patent (USP) 4,482,687; 4,277,372; 3,642,746; With 3,642,772, European patent 131,832): as the properties-correcting agent (as United States Patent (USP) 4,158,642 and 4,148,756) of promotor; As solvent (United States Patent (USP) 4,477,639 and 4,518,706).Yet, resemble the present invention and like this each step is carried out special combination, make catalyzer, the Shang Weiyou report with excellent performance.
The present invention is a kind of solid alpha-olefin polymerization catalyst component that is insoluble to hydro carbons with high reactivity, high stereospecificity and good form performance, contains the product that the following step makes: A) prepare a kind of solution that contains the magnesium component with magnesiumcarbonate or magnesium carboxylates; B) handle this magniferous solution with a kind of halogenide and a kind of organosilane of transition metal, from this solution, be settled out solid particulate; C) this solid particulate of redeposition in the mixture that contains a kind of cyclic ethers; D) handle through reppd particle with a kind of transistion metal compound and a kind of electron donor.
The present invention is based on United States Patent (USP) 4,540,679 described a kind of soluble magnesium components.At first, in the presence of organosilane, handle this soluble magnesium component with halogenated titanium, form a kind of solid precipitation, this precipitation has the granularity of homogeneous, and the type of used organosilane is RnSiR ' 4-n, n=0 to 4 wherein, R=hydrogen, alkyl, alkoxyl group, chloro alkyl or aryl, R '=OR or Cl.
Another aspect of the present invention is found above-mentioned solid precipitation (THF) in containing the solution of cyclic ethers as in tetrahydrofuran solution, and redeposition can make catalyzer form and be improved.Solid particulate narrow particle size distribution behind the redeposition, the catalyzer of formation has very high activity and stereospecificity, and can obtain high bulk density, particularly bulk density from about 25Ibs/ft 3Be increased to 28-30Ibs/ft 3Be the catalyst component that obtains being suitable for, with above-mentioned through reppd solid in the presence of electron donor, use the Ti(IV) component handles.Find to adopt two-step process can prepare fabulous catalyzer, promptly use earlier the Ti(IV) component handles the solid through the redeposition processing, the Ti(V of the product after the processing) mixture of component and a kind of electron donor handles again.
The preparation method of catalyst component of the present invention is as follows: handle magnesiumcarbonate or carboxylic ester magnesium component with transistion metal compound in hydrocarbon medium, post precipitation obtains initial solid material, and the preferred practice is to carry out above-mentioned processing in the presence of organic silane compound.Initial precipitated solid is redeposition in containing the medium of cyclic ethers, as in tetrahydrofuran (THF) (THF), the solid particulate of the homogeneous that makes, the particle that obtains is with suitable Ti(IV) compound and electron donor handle again, promptly obtain olefin polymerization catalyst components, preferred treatment process is to use earlier the Ti(IV) compound handles the redeposition solid particulate in thinner, use the Ti(IV then) compound and electron donor handle again.This catalyst component combines with suitable alkylaluminium cpd, and adds suitable modified compound, has promptly formed a kind of catalyst system that is used for olefin polymerization, particularly polypropylene.The polymer beads of Unusually narrow particle size distribution be can obtain with catalyzer of the present invention, high yield and high stereoselectivity obtained simultaneously.
One aspect of the present invention is the soluble magnesium component that contains of preparation.
The soluble magnesiumcarbonate and the magnesium carboxylates that are used for the present invention were once narrated in following two pieces of documents: United States Patent (USP) 4,540,679; With on June 6th, 1985 application, u.s. patent application serial number 741,858, transferred same transferee, the present invention both as reference.Use the carbon dioxide treatment magnesium compound in suitable diluent, promptly obtain the solution of magnesiumcarbonate and magnesium carboxylates, preferred way is to carry out above-mentioned processing in the presence of suitable solvent, carries out in the presence of at a kind of alcohol.For example,,, add carbonic acid gas,, promptly obtain ethyl carbonate magnesium to the magnesium ethylate dissolving as magnesium ethylate being suspended in a kind of medium of alcohol with alkoxyl magnesium.The solution that equally also can use alkyl magnesium and alcohol to form.
Can be used for typical alcoholization magnesium of the present invention comprises: Mg(OCH 3) 2, Mg(OC 2H 5) 2, Mg(OC 4H 9) 2, Mg(OC 6H 5) 2, Mg(OC 6H 13) 2, Mg(OC 9H 19) 2, Mg(OC 10H 7) 2, Mg(OC 12H 9) 2, Mg(OC 12H 25) 2, Mg(OC 16H 33) 2, Mg(OC 20H 41) 2, Mg(OCH 3) (OC 2H 5), Mg(OCH 3) (OC 6H 13), Mg(OC 2H 5) (OC 8H 17), Mg(OC 6H 13) (OC 20H 41), Mg(OC 3H 7) (OC 10H 7), Mg(OC 2H 4Cl) 2And Mg(OC 16H 33) (OC 18H 37).If need also can use the mixture of alcoholization magnesium.In addition, also can use alcoholization magnesium and other alkaline-earth metal alkoxy compound, the basic metal alcoxylates, a spot of other suitable metallic salt, as the alcoholate of lanthanum and lanthanide series metal, magnesium halide, hydroxyhalide, the mixture that carboxylate salt etc. form.When with the reaction of carbonic acid gas in alcohol during as suspension agent, alkyl alcoholization magnesium is suitable with the function of alcoholization magnesium, because alkyl alcoholization magnesium is converted into Mg(OR in alcohol) (OR ').Corresponding M n(II) and the Fe(II) compound, as Mn(OCH 3) 2, and Fe(OCH 3) 2, also being considered to II with Mg() and compound is suitable.
When adding carbonic acid gas in the inertia suspension agent, alkyl alcoholization magnesium is converted into the salt of alkyl magnesiumcarbonate.Can use the spheric alkoxyl magnesium if desired, particularly when carbonation is not used alcoholic medium on.The reaction of alcoholization magnesium compound and carbonic acid gas can be represented
Figure 87105136_IMG1
Wherein R is the alkyl of 1-20 carbon atom.
In addition, the present invention also can use the solution that alkyl magnesium compound and carbonic acid gas form.Alkyl magnesium compound and carbonic acid gas are anti-just to be formed
Wherein R is the alkyl of 1-20 carbon atom.Have been found that sulfurous gas can replace carbonic acid gas, form the alkyl magnesium sulfite, the latter can replace alkyl magnesiumcarbonate.
Its structure of alkyl magnesium compound that is used for the present invention is: R-Mg-Q, wherein Q is a hydrogen, halogen or R ' (each R ' alkyl that contains 1-20 carbon atom of respectively doing for oneself.) the typical alkyl magnesium compound that is used for the present invention comprises:
Mg(CH 3) 2, Mg(C 2H 5) 2, Mg(C 4H 9) 2, Mg(C 6H 5) 2, Mg(C 6H 13) 2, Mg(C 9H 19) 2, Mg(C 10H 7) 2, Mg(C 12H 9) 2, Mg(C 12H 25) 2, Mg(C 16H 33) 2, Mg(C 20H 41) 2, Mg(CH 3) (C 2H 5), Mg(CH 3) (C 6H 13), Mg(C 2H 5) (C 8H 17), Mg(C 6H 13) (C 20H 41), Mg(C 3H 7) (C 10H 7), Mg(C 2H 4Cl) 2(C 16H 3B) (C 18H 37), Mg(C 2H 5) (H), Mg(C 2H 5) (Cl), Mg(C 2H 5) (Br), etc.If need also can use the mixture of alkyl magnesium compound.
The preferred dialkyl magnesium compound that is used for the present invention is that those molecular formula are Mg(R ') 2Compound, wherein R ' is by above-mentioned definition.Use molecular formula to be Mg(R ') the alkyl halogenated magnesium compound of Q ', can aspect catalytic activity and stereospecificity, obtain fabulous result, wherein R ' is one 1 alkyl to about 18 carbon atoms, one 6 aryl or one 7 alkaryl or aralkyl to about 12 carbon atoms to about 12 carbon atoms, Q ' is a chlorine or bromine.
The alcohols that is used for solvation magnesiumcarbonate and magnesium carboxylates comprises that those structural formulas are the alcohol radical of HOR ', wherein R ' is one 1 alkyl to about 18 carbon atoms, one 6 aryl, or one 7 alkaryl or aralkyl to about 12 carbon atoms to about 12 carbon atoms.Particularly can use one or more alcohols that contain 1 to 12 carbon atom such as methyl alcohol, ethanol, propyl alcohol, Virahol, butyl alcohol-tert, ring ethanol, 2-Ethylhexyl Alcohol, dodecanol etc., wherein preferred alcohol is 2-ethyl-1-hexanol.
Another aspect of the present invention is more excellent for halogenated titanium (IV) processing magnesiumcarbonate and magnesium carboxylates solution, to be settled out initial solid constituent with transition metal halide.Preferably use titanium tetrachloride.This processing better is to carry out in suitable diluent, and is preferably under the existence of organosilane and carries out.
When the preparation catalyst component, add suitable silane, can obtain good form.Be not contain too much powder or big particle in the size distribution.The present invention is being settled out in the solid step from soluble magnesium component, adopts suitable organosilane reagent, and its molecular formula is RnSiR ' 4-n, n=0 to 4 wherein, R is hydrogen or an alkyl, the alkoxyl group that contains one to about ten carbon atoms, haloalkyl or aryl, or contain a halo silyl or a haloalkyl silyl to about eight carbon atoms, R ' is OR or halogen.Especially, R is an alkyl or contains one to about eight carbon atoms and a chloro alkyl to about four chlorine atoms that R ' is that chlorine or one arrives four carbon atom-OR base.The organosilane that is suitable for can contain different R ' groups.Can use the mixture of organosilane.Preferred organosilane comprises: trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane(DMCS) and tetraethoxysilane.
When preparation stereospecificity supported catalysts component of the present invention, the general soluble magnesium component that contains, halogenated titanium (IV) component and organosilane component by following magnesium/titanium atom than contacting: be at least about 0.3: 1, preferably, preferred from 0.5: 1 to about 3: 1 from 0.4: 1 to about 20: 1.General Si/Ti atomic ratio can be from about 0.1: 1 to about 2.0: 1, preferably from about 0.3: 1 to about 1: 1.
Another aspect of the present invention is with initial precipitated solid redeposition in containing the solution of cyclic ethers.In typical redeposition process, initial solid is dissolved in the cyclic ethers solution fully, then the solid redeposition is obtained the particle of size homogeneous.Preferred ether is tetrahydrofuran (THF), and other cyclic ethers that is suitable for that can dissolve initial solid constituent also can use, as tetrahydropyrans, 2-methyltetrahydrofuran.Thioether class such as tetramethylene sulfide also can use, and in some cases, as use 2,2,5,5, and-tetrahydrofuran (THF) and tetrahydropyrans-2-methyl alcohol will be heated to about 130-185 °F and just can produce redeposition.Also can use other compound of suitable function, promptly those can dissolve initial solid, and carry out the compound of the uniform solid particulate that obtains behind the redeposition therein, as the oxidation cyclic ethylene, and pimelinketone, vinyl acetic monomer and phenyl acetate.The mixture that is suitable for compound also can use.
Another aspect of the present invention is in the presence of suitable electron donor, with the reppd solid of titanium (IV) compound treatment.The preferred practice is to adopt and two step method, selects for use titanium (IV) component to handle the redeposition solid, uses the Ti(IV then) component and suitable electron donor processing.Though generally using the Ti(IV) before component and electron donor carried out handling the second time, solid was separated from primary titaniferous solution, with the Ti(IV) alternation response can take place in component redeposition solid, adds electron donor simultaneously.
When preparation stereospecificity carried catalyst component, the organic electron donor that adopts normally contains the organic compound of oxygen, nitrogen, sulphur and the phosphorus of one or more atoms, this compound comprises organic acid, organic acid acetic, alcohol, ether, aldehyde, ketone, amine, amine oxide, acid amides, the ester class of mercaptan and various phosphoric acid and amides etc.If need to use the mixture of organic electron donor.The typical spendable oxygen electron donor compound that contains is organic acid and ester class.Can use and contain 1 to about 20 carbon atoms and 1 organic acid to about 4 carboxyls.
Preferred electron donor compound comprises the aromatic esters class.Preferred organic electron donor of the present invention is aromatics monocarboxylic acid and dicarboxylic acid and the aromatics monocarboxylic acid that is replaced by halogen, hydroxyl, oxygen base, alkyl, alkoxyl group, aryl and aryloxy and the C of dicarboxylic acid 1-C 6Alkyl esters, wherein preferably alkyl contains 1 phenylformic acid alkyl ester and halogeno-benzene methyl ether alkyl ester to about 6 carbon atoms, as methyl benzoate, bromobenzene methyl-formiate, ethyl benzoate, chlorinated benzene ethyl formate, bromobenzene ethyl formate, butyl benzoate, benzene methyl isobutyl ester, hexyl-benzoate and phenylformic acid cyclohexanol.Other preferred esters include ethyl anisate and methyl p-methyl benzoate.Particularly preferred aromatic ester is a bialkyl ortho phthalate, and wherein alkyl contains two to about ten carbon atoms.The example of preferred phthalic ester is as diisobutyl phthalate, diethyl phthalate, phthalic acid acetoacetic ester, butyl ester and n-butyl phthalate.
Titanium (IV) compound that the present invention is used to handle the redeposition solid particulate is halogenated titanium and halogenation alcoholization titanium, and wherein each alcohol radical contains 1 to about 20 carbon atoms.Can use the mixture of titanium compound if desired.Preferred titanium compound is that halogenide and each alcohol radical contain 1 halogenated alcoholate to about 8 carbon atoms.The example of this compounds comprises: TiCl 4, TiBr 4, Ti(OCH 3) Cl 3, Ti(OC 2C 5) Cl 3, Ti(OC 4H 9) Cl 3, Ti(OC 6H 5) Cl 3, Ti(OC 6H 13) Br 3, Ti(OC 8H 17) Cl 3, Ti(OCH 3) 2Br 2, Ti(OC 2H 5) 2Cl 2, Ti(OC 6H 13) 2Cl 2, Ti(OC 3H 17) 2Br 2, Ti(OCH 3) 3Br, Ti(OC 2H 5) 3Cl, Ti(OC 4H 9) 3Cl, Ti(OC 6H 13) 3Br and Ti(OC 8H 17) 3Cl, titanium tetrahalide, particularly titanium tetrachloride (Tl 4Cl) be most preferred.
Be used to prepare the electron donor component of solid catalytic ingredient, its amount ranges is: 0.001 mole to about 1.0 moles of every grammeatom titanium, preferred consumption is 0.005 mole to about 0.8 mole of every grammeatom titanium, when this ratio was about 0.01 mole to about 0.6 mole of every grammeatom titanium, the result of acquisition was best.
Be applicable to that typically thinner of the present invention is aromatics or the liquid that replaces aromatics, also can use other hydrocarbon liquids.Aromatic hydrocarbon, as toluene, substituted arene as chlorobenzene, has been found that and can use.Other thinner that is suitable for is the mixture of halogenated aryl hydrocarbon such as chloro or halogenated aryl hydrocarbon such as chlorobenzene and halogenated aliphatic hydrocarbon such as ethylene dichloride.Also can use the aliphatic hydrocrbon such as the kerosene of higher.Can use mixed diluent, a kind of suitable diluent composition is Isopar G, and it is 156-176 a ℃ of boiling point, on average contains the isoparaffin component of 10 carbon.Suitable diluent should have sufficiently high boiling point, promoting the carrying out of reaction, and the catalyst performance that generates is not had adverse influence.
Other thinner example that is suitable for comprises: alkane such as hexane, hexanaphthene, ethylcyclohexane, heptane, octane, nonane, decane, undecane etc.; Halogenated alkane is as 1, the 2-ethylene dichloride, and 1,1, the 2-ethylene dichloride, tetrachloro is for carbon etc.; Aromatic hydrocarbons such as benzene,toluene,xylene and ethylbenzene; Halo and hydrogenation of aromatics class such as chlorobenzene ,-dichlorobenzene.
Because catalyst component is very sensitive to catalyzer poison such as water, oxygen and carbon monoxide, the preparation of catalyst component is carried out in the presence of this class material not having basically.In at rare gas element, as nitrogen or argon gas, or in 2-alkene, be prepared reaction, can get rid of catalyzer poison.As mentioned above, all thinners that use are carried out purifying, also help from preparation system, to get rid of poisonous substance.
The solid reaction product that obtains by above-mentioned preparation process, can be used as catalyst component, need from solid reactant, to remove the not starting raw material of complete reaction before the use, this treating processes is easy to finish, after solid isolated from thinner, with suitable solvent as getting final product with liquid hydrocarbon or hydrochloric ether washing.The preferred practice is to wash as soon as possible after finishing preparation feedback, because catalyst component and unreacted starting raw material prolong duration of contact, can produce adverse influence to the performance of catalyst component.Though and do not require, before polyreaction, the solid reaction product of above-mentioned preparation can with at least a liquid Lewis(Louis) acid contacts.This Lewis acid that the present invention uses should be liquid under treatment temp, and enough strong Lewis acidity is arranged, and impurity such as unreacted starting raw material and micro-dirt settling can be removed from the surface of above-mentioned solid reaction product.Preferred Lewis acid comprises the halogenide of III-V family metal, and these compounds are in a liquid state when temperature reaches about 170 ℃.The representative instance of this compound is: BCl 3, AlBr 3, TiCl 4, TiBr 4, SiCl 4, GeCl 4, SnCl 4, PCl 3And SbCl 5Preferred Lewis acid is TiCl 4And SiCl 4Can use the mixture of Liwis acid if desired.This Lewis acid can be used in thinner that can be miscible.
Above-mentioned solid reaction product can be with inert liquid hydrocarbon or halohydrocarbon washing, though this processing not necessarily before contacting with Lewis is sour.If carry out such washing, remove inert liq basically before then being preferably in washed solid and Lewis acid contacting.
Though the chemical structure of described catalyst component it be not immediately clear, preferably contains the titanium that the 1wt% that has an appointment arrives about 6wt% in the catalyst component, about 10wt% is to the magnesium of 25wt%, and about 45wt% is to the halogen of about 65wt%.The preferred catalyst component of the present invention's preparation contains the titanium of about 1.0wt% to about 3wt%, and about 15wt% is to the magnesium and the chlorine of about 55wt% to about 65wt% of about 21wt%.
Unusual characteristics of titaniferous component particulate by preferred process of the present invention preparation are that this particle has three-dimensional shape.
Before being used as the polymerizing catalyst component, titanium-containing catalyst component of the present invention and a kind of alpha-olefin pre-polymerization, prepolymerization reaction is under the polymeric condition, with catalyzer and organoaluminum promotor-, contact with a kind of alpha-olefin as triethyl aluminum, as contacting with propylene, preferred prepolymerization is in the presence of having such as the properties-correcting agent of silane, in a kind of unreactive hydrocarbons as in hexane, carrying out.In the prepolymer component that generates, the weight ratio of polymkeric substance/catalyzer is about 0.1: 1 to about 20: 1.Prepolymerization has formed the one layer of polymeric film around making granules of catalyst, and this tunic can improve particulate form, activity, stereospecificity and abrasion resistance usually.At United States Patent (USP) 4,579, the pre-collecting process of a kind of particularly suitable of setting forth in 836 merges among the present invention as a reference.
Titanium-containing catalyst component of the present invention contains alkylate and one or more properties-correcting agent that a kind of promotor component comprises II family or III family metal when being used for polymerization.
The molecular formula of the II family that is suitable for and the alkylide of III A family metal is MRm, and wherein M is II family or III A family metal, and each R contains 1 alkyl to about 20 carbon atoms for separately one, and m is corresponding to the valence state of M.The example of suitable metal M comprises magnesium, calcium, zinc, cadmium, aluminium plus gallium.The example that is suitable for alkyl comprises methyl, ethyl, butyl, hexyl, decyl, tetradecyl and eicosyl.
Consider from the performance of catalyst component, preferred II family and III A family metal alkyls are the alkylide of magnesium, zinc and aluminium, and wherein alkyl contains 1 to about 12 carbon atoms.The representative instance of this compounds comprises Mg(CH 3) 2, Mg(C 2H 5) 2, Mg(C 2H 5]) (C 4H 0), Mg(C 4H 9) 2, Mg(C 6H 13) 2, Mg(C 12H 25) 2, Zn(CH 3) 2, Zn(C 2H 5) 2, Zn(C 4H 9) 2, Zn(C 4H 9) (C 3H 17), Zn(C 6H 13) 2, Zn(C 12H 25) 2, Al(CH 3) 3, Al(C 2H 5) 3, Al(C 3H 7) 3, Al(C 4H 9) 3, Al(C 6H 13) 3, and Al(C 12H 25) 3, preferred being to use contains 1 alkylation magnesium, alkylation zinc or alkylation aluminium to about 6 carbon atoms.Best result is to use each alkyl to contain 1 trialkylaluminium to about 6 carbon atoms, particularly uses triethyl aluminum, triisobutyl aluminium or both mixtures.
If desired, can use the metal alkyls that has one or more halogens or hydrogenation group, as aluminium such as ethyl aluminum dichloride, aluminium diethyl monochloride, sesquialter ethylaluminium chloride, hydrogenation diisobutyls.
Carrier titanium-containing compound of the present invention and alkylaluminium cpd contain the properties-correcting agent of electron donor, preferably also have silane to be grouped together, and have promptly formed typical catalyst composition.In this catalyst composition, the aluminium/titanium atom ratio that is suitable for is about 10 to 500, preferably about 30 to 300.The mol ratio of typical aluminum compound/electron donor is about 5 to 40, and typical aluminium/the silicon compound mol ratio is about 8 to 30.
For increasing catalyst activity and stereospecificity, preferred way is to add one or more properties-correcting agent, particularly electron donor and comprise following compounds: the organo-metallic sulphurated derivatives of silane, mineral acid, hydrogen sulfide, organic acid, organic acid acetic and composition thereof.
The organic electron donor that is used as promotor properties-correcting agent among the present invention is the organic compound that contains oxygen, silicon, nitrogen, sulphur and/or phosphorus.This compounds comprises the ester class of organic acid, organic acid anhydride, organic acid acetic, alcohol, ether, aldehyde, ketone, silane, amine, amine oxide, acid amides, mercaptan, various phosphoric acid and amides etc.If need, can use the mixture of organic electron donor.
Preferred organic acid and organosilane ester are benzene methyl, halogenated benzoic acid, phthalic acid, m-phthalic acid, terephthalic acid, and these sour alkyl esters, wherein alkyl contains the carbon atom about 1 to 6, as methyl benzoate, the bromobenzene methyl-formiate, ethyl benzoate, the chlorinated benzene ethyl ester, butyl benzoate, isobutyl benzoate, methyl p-methoxybenzoate, ethyl anisate, methyl p-methyl benzoate, ethyl benzoate, benzene first cyclohexyl, diisobutyl phthalate, these compounds are bringing forth good fruit aspect active and the stereospecificity, and easy to use.
The polymerization catalyst that is used for the present invention preferably contains the silane modifier of a kind of aliphatic series or aromatics.The silane that preferably is used for promotor of the present invention comprises the silane that alkyl, aryl and/or alkoxyl group replace, and the hydrocarbyl portion in the silane contains the carbon atom about 1 to 20.Particularly preferably being molecular formula is SiR 2Silane, wherein R is that incoherent R ' or OR ', R ' contain the carbon atom about 1 to 20.Preferred aromatics silane comprises phenylbenzene dimethoxy silane, phenyltrimethoxysila,e, phenylethyl dimethoxy silane and aminomethyl phenyl dimethoxy silane.Preferred aliphatic silane comprises isobutyl-front three chlorosilane, second, isobutyl dimethoxy silane.Diisopropyl dimethoxy silane, di-tert-butyl dimethoxy silane, and tertiary butyl Trimethoxy silane.
Above-mentioned catalyzer of the present invention is applicable to the polymerization of alpha-olefin, as ethene and propylene, be best suited for the alpha-olefin stereospecific polymerization that contains 3 or a plurality of carbon atoms.As the mixture of propylene, butene-1, amylene-1,4-methylpentene-1 and hexene-1 and these alkene, and the mixture of these alkene and hexene formation.Catalyzer of the present invention to propylene, propylene to more the stereospecific polymerization of high-grade alpha-olefin is effective especially up to the ethene about 20 moles of % or one.The equal polymerization of propylene is best usefulness above-mentioned catalyst composition of the present invention at least a alpha-olefin of catalysis under polymerizing condition, can obtain the poly-alpha olefins of high-crystallinity, this polymerizing condition comprises polymerization temperature and time, the elimination of monomer pressure, catalyzer poison, the use of the additive of the selection of polymer solvent in the slurry polymerization, controlling polymers molecular weight and the condition of knowledge that other those skilled in the art understand, the present invention can adopt the method for slurry polymerization, mass polymerization and vapour phase polymerization.
Catalyst consumption changes with the difference of polymerizing condition, as poly-
Close the factor known to size, polymeric monomer and other those skilled in the art of selection, reactor of technology, can determine that the common amount ranges of catalyzer of the present invention is with reference to the embodiment of back: produce every gram polymkeric substance and use about 0.2 milligram to 0.02 milligram catalyzer.
No matter use which kind of polymerization process, polyreaction all should be carried out under sufficiently high temperature, to guarantee rational polymerization velocity, avoids long reactor residence time; But temperature of reaction can not be too high, because too high polymerization velocity can cause the formation of too much regio-irregular product.Be catalytic performance and the high production speed that obtains, the scope of general temperature is from about 0 ℃ to about 120 ℃, and preferred range is from about 20 ℃ to about 95 ℃.Preferably the scope of polymerization temperature is from about 50 ℃ to about 80 ℃.
In the alpha-olefin polymerization process of the present invention, monomeric pressure is normal pressure or is higher than normal pressure.To about 60psi, in vapour phase polymerization, monomeric pressure should not be lower than the vapour pressure under the polymerization temperature of alpha-olefine polymerizing to common monomeric pressure range from about 20psi.
In batchwise polymerization operation, the polymerization time scope from about 1/2 to several hrs; In continuous polymerization process, above-mentioned polymerization time scope should be the mean residence time scope mutually.In the reaction of autoclave form, the polymerization time scope is generally from about 1 hour to about 4 hours.In slurry method, can adjust polymerization time on demand.The polymerization time scope generally is more sufficient from about 1/2 to several hrs for continuous slurry polymerization process.
In the slurry polymerization process, the thinner that is suitable for comprises: alkane and naphthenic hydrocarbon: pentane, hexane, heptane, octane, octane-iso, hexanaphthene and methylcyclohexane, alkylaromatic hydrocarbon such as toluene, dimethylbenzene, ethylbenzene, isopropyl benzene, ethyl methyl benzene, n-propylbenzene, diethylbenzene and monoalkyl naphthalene and dialkyl group naphthalene; Halogenated and hydrocarbonylation aromatic hydrocarbons is as chlorobenzene, chloronaphthalene, orthodichlorobenzene, naphthane, perhydronaphthalene; High-molecular weight liquid alkanes and composition thereof and other known thinner.Before polymer solvent uses, often need through purifying, as distill, the molecular sieve diafiltration, with the compound treatment that can remove trace impurity, as handling, or adopt other suitable method with alkylaluminium cpd.
In the gas phase polymerization process that uses catalyzer of the present invention, can adopt agitated bed reactor and fluidized-bed reactor, in following United States Patent (USP), this polymerization process is set forth: United States Patent (USP) 3,957,448; 3,965,083; 3,971,768; 3,970,611; 4,129,701; 4,101,289; 3,652,527; With 4,003,712; These documents are incorporated among the present invention as a reference.Typical gas-phase olefin polymerization reactor comprises a reaction vessel that can add olefinic monomer and catalyst component to it, comprises an agitated bed that forms polymer beads simultaneously.Usually, can catalyst component be joined in the reactor together or respectively by the one or more valve control inlets on the reactor.Recirculating gas system commonly used supply response device olefinic monomer in this system, mixes with initiate monomer after unreacted monomer is discharged from, and joins in the reactor again.A kind of quench liquid is added in the polymeric alkene by the recirculating gas system, controls the temperature of reaction, and this quench liquid can be liquid monomer.
No matter adopt which kind of polymerization technique, polyreaction all will and be removed under the condition of other catalyzer poison and carry out in anhydrous, anaerobic.
According to method of the present invention, can add the additive of controlling polymers molecular weight in the polyreaction.Those skilled in the art knows that hydrogen is a kind of additive commonly used.
Though do not need such processing usually, when polymerization is finished, maybe need to stop polymerization, when maybe needing to make catalyst deactivation of the present invention, can make catalyzer and water, alcohol, ketone, and other those skilled in the art known to the catalyst deactivation agent contact.
The product that obtains by method of the present invention is generally solid.The overwhelming majority is the isotactic poly-alpha olefins.With respect to catalyst consumption, the productive rate of polymkeric substance is enough high, does not need to isolate catalyst residue, promptly obtains spendable product.And the random content of by-products of product neutral body is very low, and product does not need separating by-products to use.Polymerisate with catalyzer of the present invention is made by extruding, injection molding, reaches other known technology processing, can make useful product.
By following examples and comparative example, described invention is described further, but summary of the invention is not limited to this.
Embodiment 1
Steps A-preparation magnesiumcarbonate solution
Churned mechanically 1 liter of reactor is housed, after the drying nitrogen purge, adds 150 gram magnesium ethylates, the mixture of 275 milliliters of 2-ethyl-1-hexanols and 300 milliliters of toluene.The rotating speed that stirs the mixture is 450rpm, and pressure carbon dioxide is 30psig, is 93 ℃ in temperature and heats three hours down.Gained solution is transferred in two liters the bottle, dilutes with 400 milliliters of toluene and 400 milliliters of n-decanes, and overall solution volume is 1520 milliliters.Every milliliter of magnesium ethylate that contains 0.10 gram equivalent of this solution.
Step B-prepares solid particulate
Under the drying nitrogen protection, in one liter of reactor, add 100 milliliters of toluene, 30 milliliters of chlorobenzenes, 9 milliliters of tetraethoxysilanes, 8.5 milliliters of titanium tetrachlorides and 100 milliliters of Isopar G(isoparaffin that on average contains 10 C, boiling point 156-176 ℃).At 26-30 ℃, rotating speed is under the 600rpm, stirs the mixture five minutes, is added in the reactor with the magnesiumcarbonate solution of syringe with 50 milliliters of steps A then, is settled out solid particulate.
Step C-redeposition solid particulate
Contain sedimentary mixture restir after five minutes, add 22 milliliters of tetrahydrofuran (THF)s (THF) rapidly with syringe, immediately mixing speed is increased to 1500rpm then, temperature rose to 60 ℃ in 15 minutes, and initial solid is dissolved in the THF solution.Add THF after about 10 minutes solid form and finish.Continue down to stir 45 minutes at 60 ℃, stop then stirring, solid leaves standstill.Decant upper strata liquid, solid is 250 milliliters twice of a toluene wash with every part.
Step D-titanium (IV) compound treatment
Step C gained solid is placed 1 liter of reactor, add 200 milliliters of chlorobenzenes and 100 milliliters of titanium tetrachlorides, mixture is in 30 minutes internal heating to 135 ℃, under the rotating speed of 1500rpm, stirred one hour, after stopping to stir, solid is left standstill, and decant upper strata liquid, gained solid add 250 milliliters of chlorobenzenes, 100 milliliters of titanium tetrachlorides and 2.1 milliliters of n-butyl phthalates, mixture is at 135 ℃, rotating speed is under the condition of 600rpm, stirs decant upper strata liquid 90 minutes, residue is 200 milliliters a toluene wash three times with every part, with every part be 200 milliliters Isopar G washing four times, with every part be 200 milliliters hexane wash twice, obtain 3.2 at last and restrain solids.This solid product analytical results is: 55.1wt% chlorine, 16.8wt% magnesium, 2.3wt% titanium, 7.3wt% n-butyl phthalate.
Embodiment 2
Similar with embodiment 1, prepare another kind of catalyst component, different is: among the step B, tetraethoxysilane adds after magnesiumcarbonate solution and titanium tetrachloride reaction, and the redeposition step is that the pressure in carbonic acid gas is to carry out under the condition of 20psig from THF.
Embodiment 3
Similar with method described in the embodiment 1, prepare another kind of catalyst component, different is: use 300 milliliters of toluene, 60 milliliters of chlorobenzenes, 18 milliliters of tetraethoxysilanes, 17.5 milliliters of titanium tetrachlorides among the step B.Obtain solid particulate redeposition in 44 milliliters of THF.Handle the redeposition solid particulate with 200 milliliters of chlorobenzenes and 42 milliliters of titanium tetrachlorides, and then handle with 300 milliliters of chlorobenzenes, 100 milliliters of titanium tetrachlorides and 4.2 milliliters of n-butyl phthalates.
Embodiment 4
Similar with method described in the embodiment 1, prepare another kind of catalyst component, different is among step D redeposition solid particulate is with 100 milliliters of chlorobenzenes, and 100 milliliters of titanium tetrachlorides and 2 milliliters of n-butyl phthalates are handled once.
Embodiment 5
Similar with method described in the embodiment 1, prepare another kind of catalyst component, different is: use 100 milliliters of toluene, 200 milliliters of chlorobenzenes, 18 milliliters of trimethylethoxysilanes and 17.5 milliliters of titanium tetrachlorides among the step B.The redeposition solid particulate is with 200 milliliters of chlorobenzenes among the step D, and 200 milliliters of titanium tetrachlorides and 5 milliliters of n-butyl phthalates are handled once.
Comparative examples A
Similar with embodiment 1, prepare another kind of catalyst component, difference is: do not use silane among the step B, the redeposition solid particulate is with 200 milliliters of chlorobenzenes among the step C, 100 milliliters of titanium tetrachlorides and 2 milliliters of n-butyl phthalates are handled once, the distribution of particle sizes of gained catalyst component is random, contains a large amount of powder and macrobead.
Comparative example B
Similar with embodiment 1 described method, prepare another group catalyzer group, difference is: the particle of step B separates after filtration, uses twice of hexane wash.In one liter of reactor, with this dried solid suspension of 6 grams in 200 milliliters of chlorobenzenes, 100 milliliters of titanium tetrachlorides and 2.5 milliliters of diisobutyl phthalates, the 800rpm rotating speed with mixed 1 hour.After stopping to stir, remove upper strata liquid, add 200 milliliters of titanium tetrachlorides, continue to stir one hour down, respectively wash three times with toluene, hexane respectively subsequently at 137 °-143 ℃.
Embodiment 6
Similar with embodiment 1 described method, prepare another kind of catalyst component, difference is: in steps A, add 30 gram magnesium ethylates and add 300 milliliters of toluene in 450 milliliters of pressure bottles.At room temperature, pressure carbon dioxide is under the 30Psig condition, gained suspension is stirred spend the night.In step B, in room temperature, rotating speed is under the condition of 600rpm, stirring is by the formed mixture of suspension of 100 milliliters of toluene, 13 milliliters of trimethylethoxysilanes, 8.75 milliliters of titanium tetrachlorides, 100 milliliters of Isopar G and 50 milliliters of steps A, add 22 milliliters of THF after about 5 minutes, obtain clear solution.In about 15 minutes temperature is risen to 66 ℃, be settled out solid at leisure after about 10 minutes, temperature kept 30 minutes at 66 ℃.
Embodiment 7
Similar with embodiment 1 described method, prepare another kind of catalyst component, difference is: add 10 gram magnesium ethylates in one liter of reactor, 200 milliliters of chlorobenzenes, 100 milliliters of toluene, 18 milliliters of tetraethoxysilanes, 15 milliliters of 2-ethyl-1-hexanols and 17.5 milliliters of titanium tetrachlorides.Gained suspension in room temperature, stir under, with 44 milliliters of THF reactions, obtain a kind of clear solution.Carry out according to the step of embodiment 1 later.
Comparative example C
Similar to embodiment 7 described methods, prepare another kind of catalyst component, difference is: do not add 2-ethyl-1-hexanol, though use pulverous magnesium ethylate, this solid is dissolved in THF still can not be in former embodiment, even adds 5% THF and can not dissolve.
Embodiment 8
Similar to the method described in the embodiment 1, prepare another kind of catalyst component, difference is: use 170 milliliters of toluene, 35 milliliters of Isopar G, 20.5 milliliters of tetraethoxysilanes, 19.4 milliliters of titanium tetrachlorides and 114 milliliters of magniferous solution in step B.The gained solid particulate is redeposition in 50 milliliters of tetrahydrofuran (THF)s.The redeposition solid particulate is handled with 200 milliliters of toluene and 100 milliliters of titanium tetrachlorides earlier, uses 250 milliliters of toluene then, and 100 milliliters of titanium tetrachlorides and 4.2 milliliters of n-butyl phthalates are handled.The solid that obtains obtains the uniform spherical particle with hot toluene washing three times, and mean particle size is 18 microns.
Embodiment 9
Similar to embodiment 8 described methods, prepare another kind of catalyst component, difference is: the stainless autoclave that adopts three liters of strap clamp covers wherein also is equipped with traverse baffle and magnetic stirring apparatus as reactor.Reactant is 1190 milliliters of toluene, 350 milliliters of Isopar G, and 144 milliliters of tetraethoxysilanes, 136 milliliters of titanium tetrachlorides and 798 milliliters contain magnesium solution.The gained solid particulate is redeposition in 350 milliliters of THF, and the redeposition solid particulate is handled with 1400 milliliters of chlorobenzenes and 700 milliliters of titanium tetrachlorides earlier, uses 1750 milliliters of chlorobenzenes then, and 700 milliliters of titanium tetrachlorides and 29.4 milliliters of n-butyl phthalates are handled.The gained solid is 500 milliliters toluene, Isopar G, a hexane wash with every part respectively, and obtaining the solid total amount at last is 75 grams.
Vapour phase polymerization:
With the titaniferous component for preparing among the embodiment 1-9, carry out gas-phase propylene polymerization at a series of intermittence, react in 2.5 liters of reactors and carry out, temperature is 71 ℃, pressure is 300psig, hydrogeneous 36 mmoles, the 40rpm rotating speed stirs, and the reaction times is 2 hours.Triethyl aluminum (TEA) is as promotor, and has dimethoxydiphenylsilane (DPDMSi) properties-correcting agent.In reactor, be sequentially added into TEA/ properties-correcting agent, titanium component, hydrogen and propylene.The results are shown in the table I.
" productive rate " (polymkeric substance gram number that every gram solid catalytic ingredient is produced) can be determined by the Mg content of analyzing in the polymerisate, also can determine by producing the used solid catalyst weight of polymkeric substance sometimes.The measuring method of " extractable content " is: the extracting four to six hours in the ebullient normal hexane of exsiccant polymer powder sample, measure the weight loss of exsiccant polymer samples then.
The table II
Polymer particle size distributes
Granularity accounts for the percentage ratio of gross weight
(micron) (embodiment 1)
＞850 3.8
600-850 27.5
425-600 56.2
150-425 12.3
＜150 0.2
Embodiment 10-12
Similar to the method described in the embodiment 1, prepare another kind of catalyst component (embodiment 10).In the steps A, with 11.4 gram magnesium ethylates, 175 milliliters of toluene and 21 milliliters of 2-ethyl-1-hexanols are added in 450 milliliters the pressure bottle, and gained suspension is under the carbon dioxide conditions of room temperature, 25psig pressure, and stirring is spent the night.Among the step B, under the rotating speed of room temperature, 1500rpm, with 80 milliliters of toluene, 20.5 milliliters of tetraethoxysilanes, all reactor content of 19.4 milliliters of titanium tetrachlorides and 35 milliliters of Isopar G and steps A stirred five minutes.Among the step C, use 50 milliliters THF in the redeposition process, the gained solid is 80 milliliters twice of a toluene wash with every part.Among the step D, the consumption of n-butyl phthalate is 4.2 milliliters, and products therefrom is 80 milliliters a toluene wash twice with every part, and every part is 80 milliliters Isopar G washing three times, and every part is 80 milliliters twice of hexane wash.Obtaining the solid total amount at last is 2.8 grams.The analytical results of solid product is: 60.4wt% chlorine 19.7wt% magnesium, 19.2wt% titanium, 9.0wt% n-butyl phthalate and 1.2wt%THF.
Method similar to Example 10, prepare another group catalyst component (embodiment 11), difference is: replace 200 milliliters of chlorobenzenes to do to handle for the first time with 200 milliliters of toluene among the step D, obtaining the solid total amount at last is 7.4 grams, and the solid product analytical results is: 61.0wt% chlorine, 20.1wt% magnesium, 1.87wt% titanium, 9.6wt% n-butyl phthalate and 0.2wt%THF.
Method similar to Example 10 prepares another kind of catalyst component, (embodiment 12).Obtaining the solid total amount is 9.0 grams, and the solid product analytical results is: 58.0wt% chlorine, 16.8wt% magnesium, 1.65wt% titanium and 10.2wt% n-butyl phthalate.
The titanium-containing catalyst component for preparing above is used for the propylene interrupter method polymerization of hexane slurries.In two liter Pa Er reactors, add 650 milliliters of hexanes, the propylene of 150psig, the hydrogen of 4psig.With about 15 milligrams titanium-containing catalyst component and the triethyl aluminum (TEA) that contains dimethoxydiphenylsilane (DPDMSi) is main co-catalyst system, is used for polymerization experiment, and the reaction times is two hours, and temperature is 71 ℃.Experimental result is listed in the table III.The polymer particle size that is obtained by the polymerization of embodiment 10-12 distributes and lists in the table IV.
Embodiment 13-16
Intermittent bulk polyreaction with the titaniferous component catalyst series of preparation among the embodiment 1.Two liters of Pa Er reactors add hydrogen (10psig) and 1000 milliliters of liquid propylene after propylene purifies.Use 300 milliliters of propylene again, the catalyst/co-catalyst/modifier package that is pre-mixed is flushed in the reactor, the TEA/DPDMSi/Ti mol ratio is 200/10/1.React after one hour, add 10 milligrams of titaniferous components, react after two hours, add 8 milligrams of titaniferous components again, the gram closed reactor is heated to 70 ℃, and reaction is one to two hours under 480psig.The results are shown in the table V.
Embodiment 17
Press embodiment 1 described method, preparation magnesiumcarbonate solution in one liter of reactor.In nitrogen atmosphere, in one liter of reactor, add 150 milliliters of toluene, 35 milligrams of Isopar G, 20.5 milliliters of tetraethoxysilanes and 19.4 milliliters of titanium tetrachlorides.Mixture is remained on 24-29 ℃, under the 600rpm rotating speed, stirred five minutes, behind the formation solid, mixture restir five minutes.Add the THF(50 milliliter rapidly with syringe), initial solid all dissolves.Mixing speed is increased to 1200rpm, makes temperature rise to 60 ℃ in 15 minutes and adds after THF10 minute, occurs solid in the mixture at leisure, and solid forms and finishes after about 5 minutes.60 ℃ of heating one hour, stop then stirring, leave standstill the solid about ten minutes of gained.In nitrogen atmosphere, 38-50 ℃ of following decant upper strata liquid, solid is 50 milliliters twice of a toluene wash with every part.Solid after the washing adds 125 milliliters of toluene and 50 milliliters of titanium tetrachlorides, and the gained mixture is in 30 minutes internal heating to 135 ℃.At 120 ℃, under the 800rpm rotating speed, mixture was stirred one hour, stop then stirring, leave standstill solid, decant upper strata liquid.Solid adds 150 milliliters of toluene, and 50 milliliters of titanium tetrachlorides and 2.8 milliliters of n-butyl phthalates at 120 ℃, stir mixture heating up 90 minutes under the 800rpm rotating speed.Stop to stir, solid leaves standstill, decant upper strata liquid.Add 95 milliliters of toluene again, mixture stirring and refluxing 20 minutes.Stop to stir, solid leaves standstill, decant upper strata liquid.Add 125 milliliters of titanium tetrachlorides again, stir gained suspension, reflux 20 minutes, the gained solid is 50 milliliters a hexane wash four times with every part, solid hexane suspension is transferred to passed through in the loft drier that nitrogen purge crosses.Solid catalytic ingredient is filtered drying.
The part catalyzer is used in the propylene polymerization that is carried out as embodiment 1-9.The TEA/DPDMSi/Ti mol ratio is 200/20/1.Polymerization result is: productive rate 22.125g/g; Extractable content 1.6wt%; Bulk density 28.51bs/ft 3; With melt flow rate 4.6g/10 minute.
Embodiment 18
Similar to embodiment 1 method, prepare another kind of catalyst component.Difference is: the solid of step C preparation adds 200 milliliters of toluene and 100 milliliters of titanium tetrachlorides, under 110 ℃ of 500rpm rotating speeds, the gained mixture is stirred one hour.The mixture that in mixture, slowly adds 50 milliliter of four benzene and 3.0 milliliters of n-butyl phthalates.Mixture stirred 1.5 hours, and decant upper strata liquid adds 150 milliliters of toluene again, when temperature reaches 93-96 ℃, mixture was stirred 30 minutes.Upper strata liquid decant is gone out again, add 125 milliliters of toluene, when temperature reaches 110 ℃ mixture was stirred 30 minutes, decant upper strata liquid, the solid that stays are 100 milliliters hexane wash four times with every part with 100 milliliters of toluene wash once.With solid filtering, drying.Adopt vapour phase polymerization technology at foregoing intermittence, this catalyst component is carried out propylene polymerization experiment, TEA/DPDMSi/Ti mol ratio=200/20/1.Polymerization result is: productive rate=24125g/g, extractable content=1.8wt%; Bulk density=27.91bs/ft 3, MFR=4.1.
Embodiment 19
Similar with the method for embodiment 4, prepare another kind of catalyst component, difference is: replace THF with 20 milliliters of tetrachloro pyrans.The clear propylene polymerization of slurries, TEA/DPDMSi/Ti mol ratio are 200/10/1, polymerization result: productive rate 7200g/g; Extractable content 0.4wt%.
Embodiment 20
In the exsiccant nitrogen atmosphere, in 450 milliliters of pressure bottles that have magnetic stirring bar, add 11.25 gram magnesium ethylates.Bottle is with on the rubbery plug lid, adds the 2-ethyl 1-hexanol of 120 milliliters of toluene and 20 milliliters with syringe.Adding carbonic acid gas to pressure by syringe needle in reaction flask is 25psig, with mixture stir about 16 hours under pressure carbon dioxide, with carbonic acid gas emptying, adding hexane to cumulative volume in reaction flask is 300 milliliters, and content is preserved (solution A) in nitrogen.Be used for dry nitrogen purge and add 50 milliliters of toluene then, 5.6 milliliters of titanium tetrachlorides and 13.6 milliliters of trimethylchlorosilanes by 500 milliliters of resin bottles that 125 milliliters of dropping funnels are arranged.Obtain bright-coloured orange solution (solution B), with this solution of glass stick violent stirring.
In 500 milliliters of resin bottles that have a dropping funnel, load onto mechanical stirring and temperature probe, behind nitrogen wash, with an intubate 100 ml soln A are joined in the resin bottle, under the stirring of 450rpm rotating speed, orange solution B was added in the resin bottle in 35-60 minute then.Solution begins to become lacteous, is white then, is faint yellow at last, after dropwising, continues to stir one hour under 60 ℃, 450rpm rotating speed.After stopping heating, solid is left standstill decant upper strata liquid.Solid is 75 milliliters a toluene wash three times with every part, and per minute is 100 milliliters a hexane wash twice, with the solid filtering after the washing, drying.Productive rate is 3.5 grams.
Resin bottle is loaded onto mechanical stirring, adds the exsiccant solid, 150 milliliters of chlorobenzenes and 50 milli milliliter titanium tetrachlorides.At rotating speed is under the stirring of 450rpm, drips 1.3 milliliters of phthalic acid two isobutyl fat in mixture.Improve temperature of reaction, mixture refluxed 90 minutes in 130 ℃.Stop heating, mixture was stirred about three minutes, leave standstill then about five minutes.The upper strata liquid of decant heat, remaining solid is 75 milliliters a toluene wash three times with every part, is 100 milliliters twice of hexane wash with every part.With gained solid (2.2 gram) filtration, drying.With this solid catalytic ingredient, carry out slurry polymerization test according to the method among the embodiment 10-12, experimental result is listed in the table VI.
Comparative Example F, G
Similar with the method described in the embodiment 20, prepare a kind of catalyst component (Comparative Example F), difference is: solution B contains careful trimethylchlorosilane and the 50 milliliters of toluene of 39.0 millis.Similar with the method described in the experimental example 20, prepare another kind of catalyst component, (comparative example G), difference is: solution B contains 8.44 milliliters of titanium tetrachlorides and 50 milliliters of toluene.Solid catalytic ingredient is carried out the slurry polymerization experiment, the results are shown in the table VI described in polymerization process such as the embodiment 10-12.
Embodiment 21
Similar with embodiment 17 described methods, prepare a kind of catalyst component.The gas phase polymerization process at intermittence that is carried out as embodiment 1-9 is adopted in the polymerization of two alkene, and different is to have used polymeric modifier second, isobutyl dimethoxy silane (DIBDMSi), TEA/DIBDMSi/Ti mol ratio=200/20/1 in polymerization.Polymerization result: productive rate=22,100g/g; Extractable content=1.4%; Bulk density=28.41bs/ft 3; MFR=4.6.
Embodiment 22
Similar with embodiment 17 described methods, prepare a kind of catalyst component, the different 2-methyltetrahydrofurans that are to use.Test with the slurry polymerization that solid catalytic ingredient carries out described in embodiment 10-12.Polymerization result: productive rate=20,162g/g; Solute=8.2%; Extractable content=2.8%; Bulk density=23.91bs/ft 3; MFR=3.8.
Embodiment 23
Similar with embodiment 20 described methods, prepare a kind of catalyst component, difference is to replace carbonic acid gas with sulfurous gas.Adopt the gas phase polymerization process at intermittence that is carried out as embodiment 1-9, polypropylene, difference is TEA/DPDMSi/Ti mol ratio=100/10/1.Polymerization result: productive rate=8,500g/g; Extractable content=1.3%; Bulk density=27.71bs/ft 3; MFR=2.2.
The table I
The vapour phase polymerization characteristic
Embodiment helps catalysis productive rate extractable content bulk density to melt molten flow rate
(sequence number) agent system (g/g) is 1bs/ft (wt%) 3(g/10 minute)
1 a 24，000 1.2 29.0 1.7
2 b 24，700 1.2 29.7 1.4
3 b 28，900 1.0 29.4 2.3
4 a 10，100 3.5 28.2 3.4
5 a 13，500 1.6 29.7 2.2
（A） a 10，100 2.0 27.2 1.6
（B） c 8，200 1.4 26.0 2.1
6 c 14，000 2.4 29.0 1.5
7 b 21，300 1.5 27.8 2.7
8 a 23，500 1.0 29.0 2.8
9 a 22，600 1.1 29.0 3.5
Co-catalyst system:
TEA/DPDMSi/Ti mol ratio: a=100/8/1
b＝200/20/1
c＝100/10/1
The table III
The slurry polymerization characteristic
Embodiment helps catalysis productive rate extractable content hexane solute bulk density
(sequence number) agent system (g/g) is (wt%) (1bs/ft (wt%) 3)
10 a 14，800 3.0 1.8 24
10 b 15，600 1.4 0.7 24
11 b 13，700 1.0 0.4 27
12 a 13，200 0.3 1.0 28
12 b 14，300 0.2 0.6 30
12 c 10，400 … 1.0 27
Co-catalyst system:
Mol ratio: a:TEA/DPDMSi=20/1 Al/Ti=125/1
b：TEA/DPDMSi＝20/1 Al/Ti＝550/1
c：TEA/DPDMSi＝10/1 Al/Ti＝550/1
The table IV
Polymer particle size distributes
Account for the percentage ratio of total amount
Granularity (micron) (embodiment 10a) (embodiment 10b) (embodiment 11)
＞850 0.5 0.3 0.4
425-850 4.6 4.1 3.5
250-425 85.9 86.8 83.8
180-250 7.5 6.8 8.2
150-180 0.8 0.6 1.7
75-150 0.4 0.6 2.0
＜150 0.2 0.8 0.3
The table V
The mass polymerization characteristic
Embodiment time productive rate extractable content bulk density melt flow rate
（hr） （g/g） （wt%） （1bs/ft 3） （g/10min）
13 1 33，300 1.9 25.0 1.4
14 1 34，000 1.8 24.7 1.2
15 2 48，800 - 24.0 -
16 2 51，900 - 22.3 -
The table VI
The slurry polymerization characteristic
Embodiment helps catalysis productive rate extractable content hexane solvend bulk density
(sequence number) agent system (g/g) is (wt%) (1bs/ft (wt%) 3)
20 a 12，300 1.2 0.5 22
20 b 11，500 1.3 1.0 23
F a 4，000 - 2.0 -
F b 3，100 7.6 6.5 -
G b 11，900 0.8 0.6 21
Co-catalyst system:
Mol ratio: a:TEA/DPDMSi=10/1 Al/Ti＞450/1
b：TEA/DPDMSi＝20/1 Al/Ti＞450/1

Claims (34)

1, a kind of solid is insoluble to the alpha-olefin polymerization catalyst component of hydro carbons, and this component is made of the product of the following step preparation:
A is by magnesiumcarbonate or a kind of solution that contains the magnesium component of magnesium carboxylates preparation;
B handles the described magnesium solution that contains with a kind of transition metal halide and a kind of organosilane, is settled out solid particulate from this solution; The molecular formula of organosilane is RnSiR ' 4-n, n=0 to 4 wherein, R is hydrogen or alkyl, haloalkyl or an aryl that contains one to about ten carbon atoms, or contains a halo silyl or a haloalkyl silyl to about eight carbon atoms, R ' is OR or halogen;
C is in this solid particulate of mixture redeposition that contains a kind of cyclic ethers;
D handles through reppd particle with a kind of transistion metal compound and a kind of electron donor.
2, according to the catalyst component of claim 1, wherein prepare magnesiumcarbonate solution by a kind of alkoxyl magnesium and carbonic acid gas.
3, according to the catalyst component of claim 2, wherein dissolve alkoxyl magnesium with a kind of alcohol.
4, according to the catalyst component of claim 1, wherein the transition metal component among the step B is a kind of titanium (IV) compound.
5, according to the catalyst component of claim 1, wherein the transition metal component among the step B is a titanium tetrachloride.
6, according to the catalyst component of claim 1, wherein the transition metal component among the step D is a titanium tetrachloride.
7, according to the catalyst component of claim 1, wherein cyclic ethers is tetrahydrofuran (THF), tetrahydropyrans or 2-methyltetrahydrofuran.
8, according to the catalyst component of claim 1, wherein organosilane is trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane(DMCS) or tetraethoxysilane.
9, according to the catalyst component of claim 1, wherein, handle the particle that makes by step C with titanium tetrachloride, then with titanium tetrachloride and a kind of electronic treatment of giving.
10, a kind of solid, be insoluble to the alpha-olefin polymerization catalyst component of hydro carbons, this component is made of the product of the following step preparation:
A prepares a kind of alcoholic solution of being made by alkoxyl magnesium and carbonic acid gas that contains the magnesium component.
B handles the described magnesium solution that contains with a kind of titanium tetrahalide and a kind of organosilane, is settled out solid particulate from this solution; The molecular formula of organosilane is RnSiR ' 4-n, n=0 to 4 wherein, R is hydrogen or alkyl, haloalkyl or an aryl that contains one to about ten carbon atoms, or contains a halo silyl or a haloalkyl silyl to about eight carbon atoms, R ' is OR or halogen;
C is this solid particulate of redeposition in the mixture that contains a kind of cyclic ethers;
D is with a kind of Ti(IV) compound treatment is through reppd particle and then with the mixture process of a kind of titanium (IV) compound and a kind of electron donor.
11, according to the catalyst component of claim 10, wherein the halogenated titanium in the steps A is a titanium tetrachloride.
12, according to the catalyst component of claim 11, wherein the cyclic ethers among the step C is a tetrahydrofuran (THF).
13, according to the catalyst component of claim 12, wherein the halogenated titanium among the step D is a titanium tetrachloride.
14, according to the catalyst component of claim 13, wherein organosilane is trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane(DMCS) or tetraethoxysilane.
15, according to the catalyst component of claim 14, wherein the electron donor among the step D is a bialkyl ortho phthalate.
16, according to the catalyst component of claim 15, wherein the electron donor among the step D is diisobutyl phthalate, diethyl phthalate or n-butyl phthalate.
17, according to the catalyst component of claim 16, wherein the alcohol in the steps A is 2-ethyl-1-hexanol, organosilane among the step B is a tetraethoxysilane, and the electron donor among the step D is n-butyl phthalate, diisobutyl phthalate or its mixture.
18, according to the catalyst component of claim 17, wherein the electron donor among the step D is a n-butyl phthalate.
19, a kind of solid, be insoluble to the alpha-olefin polymerization catalyst component of hydrocarbon, this component is made of the product of following method preparation: the alcoholic solution of handling alkyl magnesiumcarbonate with titanium tetrachloride and organosilane, be settled out solid particulate, handle the solid particulate of gained with titanium tetrachloride and a kind of electron donor; The molecular formula of organosilane is RnSiR ' 4-n, n=0 to 4 wherein, R is hydrogen or alkyl, haloalkyl or an aryl that contains one to about ten carbon atoms, or contains a halo silyl or a haloalkyl silyl to about eight carbon atoms, R ' is OR or halogen;
20, according to the catalyst component of claim 19, wherein organosilane is a trimethylchlorosilane, dimethyldichlorosilane(DMCS) or tetraethoxysilane.
21, according to the catalyst component of claim 19, wherein electron donor is a bialkyl ortho phthalate.
22, according to the catalyst component of claim 19, wherein electron donor is diisobutyl phthalate, diethyl phthalate or n-butyl phthalate.
23, according to the catalyst component of claim 19, wherein prepare alkyl magnesiumcarbonate solution by alkoxyl magnesium and carbonic acid gas.
24, according to the catalyst component of claim 19, wherein in 2-Ethylhexyl Alcohol, prepare alkyl magnesiumcarbonate solution with magnesium ethylate and carbonic acid gas.
25, a kind of alpha-olefin polymerization catalyst contains the described solid constituent of claim 1, a kind of alkylaluminium cpd and a kind of organosilane.
26, according to the catalyst component of claim 1, wherein the transition metal component among the step D is a kind of titanium (IV) compound.
27, according to the catalyst component of claim 13, wherein the alkoxyl magnesium in the steps A is a magnesium ethylate.
28, a kind of solid, be insoluble to the alpha-olefin polymerization catalyst component of hydrocarbon, this component is made of the product of following method preparation: the alcoholic solution of the product that usefulness titanium tetrachloride and organosilane processing alkoxyl magnesium and sulfurous gas form, be settled out solid particulate, handle the solid particulate of gained with titanium tetrachloride and a kind of electron donor; The molecular formula of organosilane is RnSiR ' 4-n, n=0 to 4 wherein, R is alkyl, haloalkyl or an aryl of hydrogen or one to about ten carbon atoms, or contains a halo silyl or a haloalkyl silyl to about eight carbon atoms, R ' is OR or halogen.
29, according to the catalyst component of claim 1, wherein the organosilane among the step B is RnSiR ' 4-n, n=0 to 4 wherein, R is a hydrogen, or for containing alkyl, the alkoxyl group of one to ten carbon atom, and haloalkyl or aryl, or be the halo silyl contain a haloalkyl silyl that arrives about eight carbon atoms, and R ' is OR or halogen.
30, according to the catalyst component of claim 10, wherein the organosilane among the step B is RnSiR ' 4-n, n=0 to 4 wherein, R is a hydrogen, or for containing alkyl, the alkoxyl group of one to ten carbon atom, and haloalkyl or aryl, or be the halo silyl contain a haloalkyl silicomethane that arrives about eight carbon atoms, and R ' is OR or halogen.
31, according to the catalyst component of claim 19, wherein the organosilane among the step B is RnSiR ' 4-n, n=0 to 4 wherein, R is a hydrogen, or for containing alkyl, the alkoxyl group of one to ten carbon atom, haloalkyl or aryl or contain a halo silyl or a haloalkyl silyl to about eight carbon atoms, R ' is OR or halogen.
32, according to the catalyst component of claim 1, wherein the cyclic ethers among the step C is a kind of thioether.
33, according to the catalyst component of claim 1, wherein the cyclic ethers among the step C is a tetramethylene sulfide, 2,2,5, and 5-tetrahydrofuran (THF) or tetrahydropyrans-2-formaldehyde.
34,, wherein use oxidation cyclic ethylene, pimelinketone, capryl acetate or phenyl acetate as reppd medium among the step C according to the catalyst component of claim 1.
CN87105136A 1986-06-17 1987-06-17 Olefin polymerization catalyst Expired CN1009934B (en)

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US87518086A 1986-06-17 1986-06-17
US875180 1986-06-17
US875,180 1986-06-17
US5543087A 1987-05-28 1987-05-28
US055430 1987-05-28
US055,430 1987-05-28

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DE3784173D1 (en) 1993-03-25
DE3784173T2 (en) 1993-06-09
CN87105136A (en) 1988-06-22
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DE3751622T2 (en) 1996-04-25

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